Blue-luminescent organic lead bromide perovskites: highly dispersible and photostable materials
The preparation of a blue-luminescent and photostable organic–inorganic hybrid perovskite with an X-ray powder diffraction spectrum consistent with a two-dimensional inorganic framework is reported. This perovskite can be produced with a high reaction yield and valuable optical properties, such as luminescence quantum yield over 20%, radiative rate constant of up to 80 × 106 s−1, and high photostability under UV light. This material remains stable as a solid, is toluene-dispersible, and can be reverted reversibly into its precursors by using dimethylformamide (DMF). Moreover, the DMF dispersion can be injected into toluene to produce a nanomaterial or be used to prepare films by spin-coatin…
Maximizing the emissive properties of CH3NH3PbBr3 perovskite nanoparticles
Highly luminescent and photostable CH3NH3PbBr3 nanoparticles have been prepared by fine-tuning the molar ratio between CH3NH3Br, PbBr2, a medium-size alkyl-chain ammonium salt, and 1-octadecene. The nanoparticles exhibit an excellent photoluminescence quantum yield (ca. 83%) and average recombination lifetime (ca. 600 ns) in toluene dispersion.
Colloids of naked CH 3 NH 3 PbBr 3 Perovskite Nanoparticles: Synthesis, Ssability, and thin solid film deposition
A novel preparation of lead halide, CH3NH3PbBr3, perovskite nanoparticle solid films from colloidal "naked" nanoparticles, that is, dispersible nanoparticles without any surfactant, is reported. The colloids are obtained by simply adding potassium ions, whose counterions are both more lipophilic and less coordinating than bromide ions, to the perovskite precursor solutions (CH3NH3Br/PbBr2 in dimethylformamide) following the reprecipitation strategy. The naked nanoparticles exhibit a low tendency to aggregate in solution, and they effectively self-assembled on a substrate by centrifugation of the colloid, leading to homogeneous nanoparticle solid films with arbitrary thickness. These results…
Creation and Annihilation of Nonradiative Recombination Centers in Polycrystalline Metal Halide Perovskites by Alternating Electric Field and Light
Metal halide perovskites are promising optoelectronic materials. Their electronic properties however are rather unstable which is often assigned to ion migration. Ion migration can be readily influenced by an electric field (EF). Here, the response of photoluminescence (PL) of individual MAPbX3 (MA = CH3NH3, X = I, Br) sub-micrometer-sized polycrystals to EF is studied. Alternating EF with frequency higher than 10 Hz is found to reversibly quench PL. It is proposed that an alternating EF when applied together with light increases ion migration. This leads to a shift in the equilibrium between creation and annihilation of defects toward higher concentration of nonradiative recombination cent…
Organic-inorganic and all-inorganic lead halide nanoparticles [Invited]
Organic-inorganic (hybrid) and all-inorganic lead halide perovskites, in particular APbX(3) where A is an organic cation (methylammonium or formamidinium) or cesium cation and X = Cl, Br, I, respectively, are of great interest in photovoltaic devices and as luminescent materials for light-emitting devices. It has recently been demonstrated that they can be prepared not only as nanoparticulate material by using the pores of mesoporous films, but also as colloidal nanoparticles, which exhibit enhanced optical properties with respect to the bulk material. We summarize here the methods reported for their preparation as well as their optical features. Experimental and theoretical studies on this…
Nontemplate Synthesis of CH3NH3PbBr3 Perovskite Nanoparticles
To date, there is no example in the literature of free, nanometer-sized, organolead halide CH3NH3PbBr3 perovskites. We report here the preparation of 6 nm-sized nanoparticles of this type by a simple and fast method based on the use of an ammonium bromide with a medium-sized chain that keeps the nanoparticles dispersed in a wide range of organic solvents. These nanoparticles can be maintained stable in the solid state as well as in concentrated solutions for more than three months, without requiring a mesoporous material. This makes it possible to prepare homogeneous thin films of these nanoparticles by spin-coating on a quartz substrate. Both the colloidal solution and the thin film emit l…
Linear assembly of lead bromide-based nanoparticles inside lead(ii) polymers prepared by mixing the precursors of both the nanoparticle and the polymer
Mixing precursors of lead(ii) polymers with those of lead bromide-based nanoparticles (CH3NH3PbBr3 perovskites or PbBr2), at room temperature and in the presence of cyclohexanemethylammonium bromide, generated colloidal nanocomposites which, when deposited on a hydrophobic surface led to long, one-dimensional, ordered and well-defined architectures. ispartof: CHEMICAL COMMUNICATIONS vol:55 issue:20 pages:2968-2971 ispartof: location:England status: published
Highly photoluminescent, dense solid films from organic-capped CH3NH3PbBr3 perovskite colloids
The preparation of densely-packed films from hybrid lead halide perovskite nanocrystals is not trivial, as during assembly into the solid state both the charge transport and photoluminescence can be substantially altered. The objective of the present study was to retain the pre-engineered confined morphologies of hybrid lead halide perovskite nanocrystals in densely-packed solid films by using short organic ligands. Therefore, the roles of the organic ligands would be to provide stable colloids and a good passivation of the nanoparticle surface, as well as to enable the efficient assembly of the nanoparticles in the solid state. We report here an effective and reproducible process to deposi…
Tuning Charge Carrier Dynamics and Surface Passivation in Organolead Halide Perovskites with Capping Ligands and Metal Oxide Interfaces
Organolead halide perovskites have emerged as exciting optoelectronic materials but a complete understanding of their photophysical properties is still lacking. Here, a morphological series of methylammonium lead bromide (MAPbBr 3 ) perovskites are studied by transient optical spectroscopies over eight orders of magnitude in timescale to investigate the effect of nanostructuring and surface states on the charge carrier dynamics. The sample preparation route and corresponding morphology changes influence the position of the optical features, recombination dynamics, excitation fluence dependence, and dramatically impact surface trap passivation. Growth of the perovskite layer in the presence …
The Luminescence of CH3NH3PbBr3Perovskite Nanoparticles Crests the Summit and Their Photostability under Wet Conditions is Enhanced
CH3 NH3 PbBr3 perovskite nanoparticles (PAD ) are prepared with a photoluminescence quantum yield of ≈100% in air atmosphere by using the quasi-spherical shaped 2-adamantylammonium bromide (ADBr) as the only capping ligand. The photostability under wet conditions of this kind of nanoparticles is enhanced by using cucurbit[7]uril-adamantylammonium (AD@CB) host-guest complexes as the capping ligand.
Linear Coassembly of Upconversion and Perovskite Nanoparticles: Sensitized Upconversion Emission of Perovskites by Lanthanide‐Doped Nanoparticles
Sensitized emission of lead halide perovskite nanoparticles (LHPNPs) can be achieved by near‐infrared (NIR) excitation of nearby lanthanide‐doped upconversion nanoparticles (UCNPs) by using a low‐cost diode laser. Here, the first preparation of linear assemblies of core and core–shell NPs, as well as linear coassemblies of LHPNPs and UCNPs, within an open peapod‐like lead sulfate shell are reported. UCNPs with a NaYF4 matrix doped with ytterbium and thulium or erbium, and with an inert shell of NaYF4 in the case of core‐shell, and all‐inorganic CsPbX3 NPs (X = halide) are chosen for these studies. Interestingly, the lead sulfate shell enhances the luminescence of the core/core– shell UCNPs …
Three independent channel nanohybrids as fluorescent probes
A properly designed pyrene-capped CdSe/ZnS nanohybrid can act as a three-channel fluorescent sensor due to the independent emission of the pyrene monomer and excimer as well as that of the nanoparticle. As proof of principle, it was tested for a simple and rapid quantification of TNT in the presence of interferents of the same chemical family.
Pyrene-Capped CdSe@ZnS Nanoparticles as Sensitive Flexible Oxygen Sensors in Non-Aqueous Media**
A flexible, highly sensitive sensor of oxygen in non-aqueous solvents is described. It consists of CdSe/ZnS nanoparticles decorated with a considerable number of pyrene units, thus making the formation of the pyrene excimer possible. The emission of the pyrene excimer and that of the nanoparticle are suitably separated from each other and also from the excitation wavelength. This sensor can be applied as a ratiometric oxygen sensor by using the linear response of the pyrene excimer lifetime combined with the linear response of the nanoparticle excited state lifetime. This nanohybrid has been assayed in seven media with different dielectric constants and viscosities over the whole oxygen con…
Organometal Halide Perovskites: Bulk Low-Dimension Materials and Nanoparticles
Organometal halide perovskites (hybrid perovskites) contain an anionic metal–halogen-semiconducting framework and charge-compensating organic cations. As hybrid materials, they combine useful properties of both organic and inorganic materials, such as plastic mechanical properties and good electronic mobility related to organic and inorganic material, respectively. They are prepared from abundant and low cost starting compounds. The perovskite stoichiometry is associated with the dimensionality of its inorganic framework, which can vary from three to zero, 3D consisting of corner-sharing MX6 octahedra, and 0D consisting of isolated octahedra. Small-sized organic cations can fit into the MX6…
Efficient Cementing of CH3NH3PbBr3Nanoparticles to Upconversion Nanoparticles Visualized by Confocal Microscopy
Upconversion-perovskite nanohybrids are prepared by assembling CH3NH3PbBr3 perovskite nanoparticles (PK) with naked NaYF4:Yb3+,Tm3+ nanoparticles (UCn) via an innovative strategy consisting of using cucurbit[7]uril (CB[7]) to anchor the perovskite nanoparticles firmly and closely to the upconversion nanoparticles, thus leading to UCn@PKCB nanohybrids. A commercial multiphoton laser scanning confocal microscope is used to demonstrate the successful assembly. This technique proves to be useful to evaluate luminescence lifetime in the range of several tens of μs and allows visualization of the extraordinarily efficient nontrivial resonance energy transfer from the upconversion nanoparticle to …
Delayed Luminescence in Lead Halide Perovskite Nanocrystals
The mechanism responsible for the extremely long photoluminescence (PL) lifetimes observed in many lead halide perovskites is still under debate. While the presence of trap states is widely accepted, the process of electron detrapping back to the emissive state has been mostly ignored, especially from deep traps as these are typically associated with nonradiative recombination. Here, we study the photophysics of methylammonium lead bromide perovskite nanocrystals (PNCs) with a photoluminescence quantum yield close to unity. We show that the lifetime of the spontaneous radiative recombination in PNCs is as short as 2 ns, which is expected considering the direct bandgap character of perovskit…